JP4888577B2 - Non-aqueous electrolyte type lithium ion secondary battery system, method for determining lithium deposition in the system, and vehicle equipped with the system - Google Patents

Non-aqueous electrolyte type lithium ion secondary battery system, method for determining lithium deposition in the system, and vehicle equipped with the system Download PDF

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JP4888577B2
JP4888577B2 JP2010091151A JP2010091151A JP4888577B2 JP 4888577 B2 JP4888577 B2 JP 4888577B2 JP 2010091151 A JP2010091151 A JP 2010091151A JP 2010091151 A JP2010091151 A JP 2010091151A JP 4888577 B2 JP4888577 B2 JP 4888577B2
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discharge amount
battery
determination
internal resistance
ion secondary
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JP2011222343A (en
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卓睦 手塚
晃生 石下
亮 真野
潤一 松本
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Toyota Motor Corp
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Priority to PCT/IB2011/000697 priority patent/WO2011128743A1/en
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    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/389—Measuring internal impedance, internal conductance or related variables
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    • G01R31/392—Determining battery ageing or deterioration, e.g. state of health
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    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/396—Acquisition or processing of data for testing or for monitoring individual cells or groups of cells within a battery
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L2200/00—Type of vehicles
    • B60L2200/26—Rail vehicles
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    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L2250/00—Driver interactions
    • B60L2250/10—Driver interactions by alarm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L58/00—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles
    • B60L58/10—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling batteries
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    • B60L58/00—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles
    • B60L58/10—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling batteries
    • B60L58/16—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling batteries responding to battery ageing, e.g. to the number of charging cycles or the state of health [SoH]
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
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Description

本発明は，非水電解液型リチウムイオン二次電池におけるリチウム析出の程度を判定するようにした非水電解液型リチウムイオン二次電池システム，そのシステムにおけるリチウム析出判定方法，および，そのシステムを搭載する車両に関する。さらに詳細には，対象の電池を解体することなく，測定したデータに基づいてリチウム析出の判定を行う非水電解液型リチウムイオン二次電池システム等に関するものである。   The present invention relates to a non-aqueous electrolyte type lithium ion secondary battery system for determining the degree of lithium deposition in a non-aqueous electrolyte type lithium ion secondary battery, a method for determining lithium deposition in the system, and the system. It relates to the vehicle to be installed. More specifically, the present invention relates to a non-aqueous electrolyte type lithium ion secondary battery system that determines lithium deposition based on measured data without disassembling a target battery.

車載用その他の非水電解液型リチウムイオン二次電池においては，その使用過程で内部に金属リチウムの析出（以下，「リチウム析出」という）が起こる場合がある。このような状態に至った電池をそのまま使用し続けていたのでは，システム本来の性能を発揮できない。従って，非水電解液型リチウムイオン二次電池におけるリチウム析出の程度を把握する必要がある。   In other non-aqueous electrolyte type lithium ion secondary batteries for in-vehicle use, metal lithium may be deposited (hereinafter referred to as “lithium deposition”) in the course of use. If you continue to use a battery that has reached such a state, the system's original performance cannot be achieved. Therefore, it is necessary to grasp the degree of lithium deposition in the non-aqueous electrolyte type lithium ion secondary battery.

このため，従来より，リチウム析出の有無を判定しようとする技術が提案されている（例えば，特許文献１参照。）。特許文献１では，走行モード時に電池の蓄電容量を算出している。そして，算出された蓄電容量を過去の蓄電容量と比較することによって，リチウム析出の有無を判定できるとされている。すなわち，リチウムが析出すると，析出がない場合に比較して蓄電容量が低下するため，蓄電容量の低下を判定することによりリチウム析出の有無を判定するとされている。   For this reason, the technique which tries to determine the presence or absence of lithium precipitation conventionally is proposed (for example, refer patent document 1). In Patent Document 1, the storage capacity of the battery is calculated in the traveling mode. Then, it is said that the presence or absence of lithium deposition can be determined by comparing the calculated storage capacity with the past storage capacity. That is, when lithium is deposited, the storage capacity is reduced as compared with the case where there is no precipitation. Therefore, it is said that the presence or absence of lithium deposition is determined by determining the decrease in the storage capacity.

特開２００９−６３５５５号公報JP 2009-63555 A

しかしながら，蓄電容量が低下する原因としては，リチウム析出によるもの以外に，経年劣化によるものがある。前記した特許文献１の技術では，これらを明確に区別することはできない。そのため，リチウム析出の判定精度が低いという問題点があった。   However, the cause of the decrease in the storage capacity is due to aging deterioration in addition to the lithium precipitation. In the technique of Patent Document 1 described above, these cannot be clearly distinguished. For this reason, there is a problem that the judgment accuracy of lithium deposition is low.

本発明は，前記した従来の技術が有する問題点を解決するためになされたものである。すなわちその課題とするところは，劣化の進行した非水電解液型リチウムイオン二次電池のリチウム析出の程度を精度よく判定できる非水電解液型リチウムイオン二次電池システム，そのシステムにおけるリチウム析出判定方法，および，そのシステムを搭載する車両を提供することにある。   The present invention has been made to solve the above-described problems of the prior art. In other words, the problem is that a non-aqueous electrolyte type lithium ion secondary battery system that can accurately determine the degree of lithium deposition in a non-aqueous electrolyte type lithium ion secondary battery that has deteriorated, and the lithium deposition judgment in that system It is to provide a method and a vehicle equipped with the system.

この課題の解決を目的としてなされた本発明の非水電解液型リチウムイオン二次電池システムは，非水電解液型リチウムイオン二次電池を予め定めた判定開始電圧から予め定めた判定終了電圧まで放電させたときの放電量（以下，「判定区間放電量」という）を取得する放電量取得部と，非水電解液型リチウムイオン二次電池の内部抵抗値を取得する内部抵抗取得部と，判定対象の非水電解液型リチウムイオン二次電池（以下，「対象電池」という）と同種の電池であってリチウム析出の起こっていないものにおける，内部抵抗値と判定区間放電量の情報との組合せを，電池の経時劣化の程度ごとに記録した相関マップと，対象電池について判定時に放電量取得部で取得した判定区間放電量と，対象電池について判定時に内部抵抗取得部で取得した内部抵抗値とを，相関マップを介して少なくとも一方を変換することにより同一の尺度上で対比して，対象電池におけるリチウム析出の程度を判定する析出判定部とを有するものである。   The nonaqueous electrolyte type lithium ion secondary battery system of the present invention made for the purpose of solving this problem is a nonaqueous electrolyte type lithium ion secondary battery from a predetermined determination start voltage to a predetermined determination end voltage. A discharge amount acquisition unit for acquiring a discharge amount when discharged (hereinafter referred to as “determination interval discharge amount”), an internal resistance acquisition unit for acquiring an internal resistance value of the non-aqueous electrolyte type lithium ion secondary battery, Information on the internal resistance value and information on the amount of discharge in the judgment section in the same type of battery as the non-aqueous electrolyte type lithium ion secondary battery (hereinafter referred to as “target battery”) that is subject to judgment, and in which lithium deposition has not occurred. The correlation is recorded for each degree of deterioration of the battery over time, the determination section discharge amount acquired by the discharge amount acquisition unit when determining the target battery, and the internal resistance acquisition unit when determining the target battery. Was the internal resistance, in contrast on the same scale by converting at least one through the correlation map, and has a determining precipitation determining unit the degree of lithium deposition in a subject cell.

本発明の非水電解液型リチウムイオン二次電池システムでは，相関マップを用いて，対象電池の判定時における，内部抵抗値と判定区間放電量の情報とを対比させ，対象電池におけるリチウム析出の程度を判定する。この相関マップは，判定対象と同種の電池で，リチウム析出が無く経年変化のみによって劣化したものについて，内部抵抗値と判定区間放電量の情報との組合せをマップ化したものである。従って，この相関マップを参照することにより，リチウム析出が無い場合の対象電池の状態を推定することができる。さらに，その推定された状態より劣化が進んでいれば，リチウムの析出によるものであると推定できる。そこで，この相関マップを介して，取得した判定区間放電量と内部抵抗値との少なくとも一方を変換して同一の尺度上で対比することにより，リチウム析出の程度を判定できる。これにより，劣化の進行した非水電解液型リチウムイオン二次電池のリチウム析出の程度を精度よく判定できる電池システムとなっている。   In the non-aqueous electrolyte type lithium ion secondary battery system of the present invention, the correlation map is used to compare the internal resistance value and the information on the discharge amount of the judgment section at the time of judgment of the target battery, and the lithium deposition of the target battery. Determine the degree. This correlation map is a map of combinations of the internal resistance value and the information on the discharge amount of the determination section for a battery of the same type as the determination target and having deteriorated only due to aging without lithium deposition. Therefore, by referring to this correlation map, the state of the target battery when there is no lithium deposition can be estimated. Furthermore, if the deterioration is more advanced than the estimated state, it can be estimated that it is due to lithium precipitation. Thus, through this correlation map, the degree of lithium deposition can be determined by converting at least one of the obtained determination section discharge amount and internal resistance value and comparing them on the same scale. As a result, the battery system can accurately determine the degree of lithium deposition of a non-aqueous electrolyte type lithium ion secondary battery that has deteriorated.

さらに本発明では，内部抵抗取得部は，放電量取得部による放電量の取得のための放電時の電流値と電圧値とから内部抵抗値の取得を行うことが望ましい。
このようなものであれば，内部抵抗値の取得のためだけに充放電を行う必要はない。 Furthermore, in the present invention, it is desirable that the internal resistance acquisition unit acquires the internal resistance value from the current value and voltage value during discharge for acquiring the discharge amount by the discharge amount acquisition unit.
In such a case, it is not necessary to perform charging / discharging only for acquiring the internal resistance value.

さらに本発明では，対象電池の新品時の判定区間放電量を取得する新品時放電量取得部を有し，析出判定部は，新品時放電量取得部が取得した判定区間放電量（以下，「新品時判定区間放電量」という）に基づいて，対象電池の判定時の判定区間放電量と，対象電池の判定時の内部抵抗値と，相関マップとの３者のうち１つを補正した上で判定を行うことが望ましい。
このようなものであれば，対象電池における新品時の性能に基づいて判定できるので，同種の電池の新品時の性能に多少のバラツキがあっても，対象電池について精度のよい判定が可能となっている。 Furthermore, in the present invention, a new battery discharge amount acquisition unit that acquires a determination battery discharge amount when the target battery is new is provided, and the deposition determination unit includes a determination discharge amount (hereinafter, “ Based on the “new product judgment section discharge amount”), one of the three of the determination section discharge amount at the time of judgment of the target battery, the internal resistance value at the time of judgment of the target battery, and the correlation map is corrected. It is desirable to make a determination at
In such a case, the determination can be made based on the performance of the target battery when it is new, so that even if there is a slight variation in the performance of the same type of battery when it is new, it is possible to make an accurate determination of the target battery. ing.

さらに本発明では，相関マップは，判定区間放電量の情報として，新品時判定区間放電量と判定区間放電量との差の値（以下，「減少放電量」という）を用いるものであり，析出判定部は，対象電池の判定時の減少放電量と，対象電池の判定時の内部抵抗値に基づいて相関マップから読み出された判定区間放電量の情報と，の差の値（以下，「追加減少分」という）に応じて，追加減少分が大きい場合はリチウム析出の程度が大きく，追加減少分が小さい場合はリチウム析出の程度が小さいと判定することが望ましい。
このようなものであれば，相関マップには，判定区間放電量の新品時からの経年劣化のみによる減少量が，内部抵抗値に対応させて記録されていることになる。従って，対象電池の判定時の内部抵抗値に基づいて相関マップから減少放電量を取得し，これと判定時の減少放電量とを比較することにより，新品時の判定区間放電量の多寡に関わらず，同一の尺度で対比させることが可能となる。これにより，リチウム析出の程度をより精度よく判定することができる。 Further, in the present invention, the correlation map uses a difference value (hereinafter referred to as “decreased discharge amount”) between the determination interval discharge amount and the determination interval discharge amount as new information as the determination interval discharge amount. The determination unit determines a difference value between the decrease discharge amount at the time of determination of the target battery and information on the determination section discharge amount read from the correlation map based on the internal resistance value at the time of determination of the target battery (hereinafter, “ According to the “additional decrease”, it is desirable to determine that the degree of lithium precipitation is large when the additional decrease is large, and that the degree of lithium precipitation is small when the additional decrease is small.
If this is the case, the correlation map records the amount of decrease in the determination section discharge amount due only to aged deterioration from the new time, corresponding to the internal resistance value. Therefore, by acquiring the reduced discharge amount from the correlation map based on the internal resistance value at the time of determination of the target battery, and comparing this with the decreased discharge amount at the time of determination, regardless of the amount of determination section discharge amount at the time of a new product. Therefore, it is possible to compare them on the same scale. Thereby, the degree of lithium deposition can be determined more accurately.

また本発明は，上記のような非水電解液型リチウムイオン二次電池システムにおいて，対象電池と同種の電池であってリチウム析出の起こっていないものにおける，内部抵抗値と判定区間放電量の情報との組合せを，電池の経時劣化の程度ごとに記録した相関マップを有し，対象電池について，判定時に判定区間放電量と内部抵抗値とを取得し，取得した判定区間放電量と，取得した内部抵抗値とを，相関マップを介して少なくとも一方を変換することにより同一の尺度上で対比して，対象電池におけるリチウム析出の程度を判定するリチウム析出判定方法にも及ぶ。   The present invention also provides information on the internal resistance value and the amount of discharge in the determination section in the non-aqueous electrolyte type lithium ion secondary battery system as described above, which is the same type of battery as the target battery and in which lithium deposition does not occur. And a correlation map recorded for each degree of deterioration of the battery over time, and for the target battery, the determination section discharge amount and the internal resistance value were acquired at the time of determination, and the acquired determination section discharge amount was acquired. The present invention also extends to a lithium deposition determination method for comparing the internal resistance value on the same scale by converting at least one of the internal resistance values via a correlation map and determining the degree of lithium deposition in the target battery.

本発明は，上記のような非水電解液型リチウムイオン二次電池システムを搭載する車両にも及ぶ。   The present invention extends to a vehicle equipped with a non-aqueous electrolyte type lithium ion secondary battery system as described above.

さらに本発明では，走行中に非水電解液型リチウムイオン二次電池の電圧値と電流値との組を測定するとともに取得された組を記憶する電圧電流取得部を有し，内部抵抗取得部は，電圧電流取得部に２以上の組が記憶されている場合には，電圧電流取得部に記憶されている組に基づいて内部抵抗値を取得するとともに，それ以外の場合には，走行しない状態で非水電解液型リチウムイオン二次電池の充放電を行うことによって複数個の電圧電流値の組を取得し，その値に基づいて内部抵抗値を取得することが望ましい。
このようなものであれば，診断のためだけの充放電をできるだけ行わないようにして，リチウム析出の程度を精度よく判定できる。 Furthermore, the present invention has a voltage / current acquisition unit for measuring a set of the voltage value and the current value of the non-aqueous electrolyte type lithium ion secondary battery during traveling and storing the acquired set, and an internal resistance acquisition unit. In the case where two or more sets are stored in the voltage / current acquisition unit, the internal resistance value is acquired based on the group stored in the voltage / current acquisition unit, and otherwise, the vehicle does not run. It is desirable to acquire a set of a plurality of voltage / current values by charging / discharging the non-aqueous electrolyte type lithium ion secondary battery in the state, and acquiring the internal resistance value based on the value.
In such a case, it is possible to accurately determine the degree of lithium deposition by performing as little charge / discharge as possible for diagnosis.

本発明の非水電解液型リチウムイオン二次電池システム，そのシステムにおけるリチウム析出判定方法，および，そのシステムを搭載する車両によれば，劣化の進行した非水電解液型リチウムイオン二次電池のリチウム析出の程度を精度よく判定できる。   According to the non-aqueous electrolyte type lithium ion secondary battery system of the present invention, the lithium deposition determination method in the system, and the vehicle equipped with the system, the deterioration of the non-aqueous electrolyte type lithium ion secondary battery is advanced. The degree of lithium deposition can be accurately determined.

本形態に係る電池システムを示すブロック図である。It is a block diagram which shows the battery system which concerns on this form. 内部抵抗値と放電量との関係を示すグラフ図である。It is a graph which shows the relationship between an internal resistance value and the amount of discharge. 電池を放電した時の電圧値と放電量との関係を示すグラフ図である。It is a graph which shows the relationship between the voltage value and discharge amount when a battery is discharged. 相関マップの例を示すグラフ図である。It is a graph which shows the example of a correlation map. 相関マップの別の使い方の例を示すグラフ図である。It is a graph which shows the example of another usage of a correlation map. 相関マップの別の使い方の例を示すグラフ図である。It is a graph which shows the example of another usage of a correlation map. 電池を搭載した車両を示す説明図である。It is explanatory drawing which shows the vehicle carrying a battery. 車両に搭載された電池における電圧値と電流値との関係を示すグラフ図である。It is a graph which shows the relationship between the voltage value and electric current value in the battery mounted in the vehicle.

以下，本発明を具体化した形態について，添付図面を参照しつつ詳細に説明する。本形態は，非水電解液型リチウムイオン二次電池（以下，単に「電池」という）を搭載している非水電解液型リチウムイオン二次電池システム（以下，単に「電池システム」という）における，リチウム析出の程度の判定のための技術である。   DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. This embodiment is a non-aqueous electrolyte type lithium ion secondary battery system (hereinafter simply referred to as “battery system”) equipped with a nonaqueous electrolyte type lithium ion secondary battery (hereinafter simply referred to as “battery”). , A technique for determining the degree of lithium deposition.

本形態に係る電池システム１０を，図１に示す。図１の電池システム１０は，判定対象である電池２１に接続されて，電池２１におけるリチウムの析出の程度を，電池２１を解体することなく判定するものである。そのために，本形態の電池システム１０は，接続された電池２１を，電圧値や電流値を制御しつつ放電させることができるようになっている。   A battery system 10 according to this embodiment is shown in FIG. The battery system 10 in FIG. 1 is connected to a battery 21 to be determined, and determines the degree of lithium deposition in the battery 21 without disassembling the battery 21. Therefore, the battery system 10 of this embodiment can discharge the connected battery 21 while controlling the voltage value and the current value.

本形態では，電池２１を，その電圧が予め決めた診断開始電圧Ｖｓから予め決めた診断終了電圧Ｖｅとなるまで放電させ，その間の電流値を積算して放電量Ｑを得る。この放電量Ｑは，電池２１の劣化により減少することが知られている。また，電池２１の状態を表す他の指標として，内部抵抗値Ｒがある。そして，内部抵抗値Ｒも，劣化によって変化することが知られている。内部抵抗値Ｒは，電池２１の劣化に伴い次第に上昇する。   In this embodiment, the battery 21 is discharged until the voltage reaches a predetermined diagnosis end voltage Ve from a predetermined diagnosis start voltage Vs, and the current value therebetween is integrated to obtain the discharge amount Q. It is known that the discharge amount Q decreases due to deterioration of the battery 21. Another index indicating the state of the battery 21 is an internal resistance value R. It is known that the internal resistance value R also changes due to deterioration. The internal resistance value R gradually increases as the battery 21 deteriorates.

電池２１が劣化する原因のうちの大きいものとして，経年劣化とリチウム析出とがある。経年劣化は，使用しなくても経年によって起きる劣化である。ただし，使用状況によってその進行の度合いは異なる。この経年劣化は，図２に示すように，放電量Ｑの減少と内部抵抗値Ｒの上昇を伴って進行する。一方，リチウム析出は，適切な使用を続ければ殆ど起きない劣化である。   Major causes of deterioration of the battery 21 include aging deterioration and lithium deposition. Aging deterioration is deterioration that occurs over time even if it is not used. However, the degree of progress varies depending on the usage situation. As shown in FIG. 2, the aging progresses with a decrease in the discharge amount Q and an increase in the internal resistance value R. On the other hand, lithium deposition is a deterioration that hardly occurs if it is properly used.

そして，本発明の発明者らは，リチウム析出の起きた電池２１における放電量Ｑの減少幅が，経年劣化による減少幅とリチウム析出に起因する減少幅との和に近いものであることを見出した。すなわち，ある基準時点からの放電量Ｑの減少幅から，その期間の経年劣化のみによる減少幅を差し引けば，リチウム析出の程度を判定できることが分かった。その一方で，内部抵抗値Ｒの上昇の程度は，リチウム析出の有無には殆ど影響されない。そのため，経年劣化のみによる放電量Ｑの減少幅は，内部抵抗値Ｒの値から推し量ることができる。そこで，内部抵抗値Ｒの値に基づいて経年劣化のみによる放電量Ｑの減少幅を推定し，これを全体の減少幅から差し引けば，リチウム析出の程度を判定することができることが分かった。   The inventors of the present invention have found that the reduction amount of the discharge amount Q in the battery 21 in which lithium deposition has occurred is close to the sum of the reduction amount due to aging and the reduction amount due to lithium deposition. It was. In other words, it was found that the degree of lithium deposition can be determined by subtracting the amount of decrease due to only aged deterioration during the period from the amount of decrease in the discharge amount Q from a certain reference point. On the other hand, the degree of increase in the internal resistance value R is hardly affected by the presence or absence of lithium deposition. Therefore, the amount of decrease in the discharge amount Q due to only aging can be estimated from the value of the internal resistance value R. Therefore, it was found that the extent of lithium deposition can be determined by estimating the reduction amount of the discharge amount Q due to only aging based on the internal resistance value R and subtracting this from the overall reduction amount.

本形態の電池システム１０は，図１に示すように，電圧制御部１１と，放電量取得部１２と，内部抵抗取得部１３と，相関マップ記憶部１４と，析出判定部１５と，新品時放電量取得部１６とを有している。さらに，相関マップ記憶部１４は，相関マップ１７を記憶するものである。本形態の電池システム１０では，電池２１の種類ごとに実験によって予め作成した相関マップ１７を，相関マップ記憶部１４に記憶している。   As shown in FIG. 1, the battery system 10 of this embodiment includes a voltage control unit 11, a discharge amount acquisition unit 12, an internal resistance acquisition unit 13, a correlation map storage unit 14, a deposition determination unit 15, and a new product. A discharge amount acquisition unit 16; Further, the correlation map storage unit 14 stores a correlation map 17. In the battery system 10 of this embodiment, the correlation map 17 created in advance by experiment for each type of the battery 21 is stored in the correlation map storage unit 14.

図１の電池システム１０において，電圧制御部１１は，接続された電池２１の電圧値を取得するとともに，放電の開始・停止等を制御するものである。本形態では電池の判定のために，予め決めた診断開始電圧Ｖｓから予め決めた診断終了電圧Ｖｅまで電池２１を放電させる。そして，本診断のための放電時には，電流値が低電流のほぼ一定値（例えば，１〜１０Ａ程度，好ましくは５Ａ程度）となるように制御しつつ放電を行う。なお，診断開始電圧Ｖｓおよび診断終了電圧Ｖｅについては特に限定はしないが，例えば，診断開始電圧ＶｓはＳＯＣ（充電状態値）６０％程度に相当する電圧，診断終了電圧ＶｅはＳＯＣ２０〜３０％程度に相当する電圧に決定しておけばよい。   In the battery system 10 of FIG. 1, the voltage control unit 11 acquires the voltage value of the connected battery 21 and controls the start / stop of discharge and the like. In this embodiment, for battery determination, the battery 21 is discharged from a predetermined diagnosis start voltage Vs to a predetermined diagnosis end voltage Ve. At the time of discharging for this diagnosis, discharging is performed while controlling the current value to be a substantially constant value of low current (for example, about 1 to 10 A, preferably about 5 A). The diagnosis start voltage Vs and the diagnosis end voltage Ve are not particularly limited. For example, the diagnosis start voltage Vs is a voltage corresponding to about 60% of SOC (charge state value), and the diagnosis end voltage Ve is about 20 to 30% of SOC. The voltage corresponding to is determined.

また，放電量取得部１２は，上記の電圧制御部１１の制御によって，診断開始電圧Ｖｓから診断終了電圧Ｖｅまで放電された期間中に，電池２１から放電された電流の電流値を時間について積算し，放電量Ｑを取得するものである。この放電量Ｑが，判定区間放電量である。本形態の放電量取得部１２によって取得される放電量Ｑは，例えば図３に示すような傾向のものである。この図で，縦軸は電池２１の電圧値，横軸はその時点までの放電量である。電池２１の状態によって，この図に示すように，得られる放電量Ｑは異なるものとなる。   In addition, the discharge amount acquisition unit 12 integrates the current value of the current discharged from the battery 21 over time during the period from the diagnosis start voltage Vs to the diagnosis end voltage Ve under the control of the voltage control unit 11. The discharge amount Q is acquired. This discharge amount Q is the determination section discharge amount. The discharge amount Q acquired by the discharge amount acquisition unit 12 of the present embodiment has a tendency as shown in FIG. 3, for example. In this figure, the vertical axis represents the voltage value of the battery 21, and the horizontal axis represents the discharge amount up to that point. Depending on the state of the battery 21, the amount of discharge Q obtained varies as shown in this figure.

また，内部抵抗取得部１３は，判定時の電池２１における内部抵抗値Ｒを取得するものである。内部抵抗値Ｒは，電池２１の充放電時の電圧値と電流値の組の値から得られる。例えば，上記のように放電量Ｑを取得するために電池２１を放電させている期間中に，電圧値と電流値との組を複数組取得して，それらから内部抵抗値Ｒを算出するようにしてもよい。   Moreover, the internal resistance acquisition part 13 acquires the internal resistance value R in the battery 21 at the time of determination. The internal resistance value R is obtained from a set of voltage value and current value when the battery 21 is charged and discharged. For example, during the period in which the battery 21 is being discharged in order to acquire the discharge amount Q as described above, a plurality of sets of voltage values and current values are acquired, and the internal resistance value R is calculated therefrom. It may be.

相関マップ記憶部１４は，図１に示すように，相関マップ１７を記憶するものである。相関マップ１７については後述する。また，析出判定部１５は，放電量取得部１２によって得られる放電量Ｑと，内部抵抗取得部１３によって得られる内部抵抗値Ｒと，相関マップ１７とを用いてリチウム析出の程度を判定するものである。その判定方法についても後述する。   The correlation map storage unit 14 stores a correlation map 17 as shown in FIG. The correlation map 17 will be described later. The precipitation determination unit 15 determines the degree of lithium precipitation using the discharge amount Q obtained by the discharge amount acquisition unit 12, the internal resistance value R obtained by the internal resistance acquisition unit 13, and the correlation map 17. It is. The determination method will also be described later.

ところで，図３に示すように放電量Ｑを比較するに当たって，その基準時点として，その電池２１の新品時というのは好ましい指標である。この時点ではリチウム析出が発生していないことが確実だからである。そこで本形態では，新品時放電量取得部１６を有し，放電量Ｑの基準値として使用するために，新品状態での当該電池２１の放電量（以下，「新品時放電量Ｑｎ」という）を取得している。この新品時放電量Ｑｎが，新品時判定区間放電量に相当する。   By the way, in comparing the discharge amount Q as shown in FIG. 3, it is a preferable index that the battery 21 is new as the reference time point. This is because it is certain that no lithium deposition has occurred at this point. Therefore, in this embodiment, the discharge amount acquisition unit 16 at the time of new article is provided, and the discharge amount of the battery 21 in the new state (hereinafter referred to as “discharge amount at new article Qn”) in order to use as a reference value of the discharge amount Q. Is getting. The new product discharge amount Qn corresponds to the new product determination section discharge amount.

図３に示したように，電池２１の状態によって，放電量取得部１２で得られる放電量Ｑは異なる。電池２１が新品である場合には，図中に太線の実線Ｌ１で示すように，同じ電圧区間の放電で最も大きい新品時放電量Ｑｎが得られる。また，図中に破線Ｌ２で示しているのは，リチウム析出を起こすことなく経年劣化のみが進行した電池（以下，「経年劣化電池２１ｒ」という）の例である。以下では，この経年劣化電池２１ｒの放電量を，経年放電量Ｑｒという。   As shown in FIG. 3, the discharge amount Q obtained by the discharge amount acquisition unit 12 varies depending on the state of the battery 21. When the battery 21 is new, as shown by the thick solid line L1 in the figure, the largest discharge amount Qn at the time of new article is obtained by discharging in the same voltage section. Also, what is indicated by a broken line L2 in the figure is an example of a battery in which only aged deterioration has progressed without causing lithium deposition (hereinafter referred to as “aged battery 21r”). Hereinafter, the discharge amount of the aged battery 21r is referred to as an aged discharge amount Qr.

また，破線Ｌ３で示しているのは，仮にリチウム析出のみによって劣化した電池というものを仮定した場合の放電量の例ＱＬである。経年劣化を起こさないことは不可能なので，実際にはこのようなことはあり得ない。いずれの例の放電量Ｑｒ，ＱＬも，新品時放電量Ｑｎより小さい。   Also, a broken line L3 shows an example QL of the discharge amount assuming that the battery is deteriorated only by lithium deposition. In fact, this is not possible because it is impossible to prevent aging. The discharge amounts Qr and QL in either example are also smaller than the discharge amount Qn when new.

また，経年劣化とリチウム析出による劣化とがともにかなり進行すると，図３中に実線Ｌ４に示すように，破線Ｌ２や破線Ｌ３よりもさらに小さい放電量ＱＭとなる。これはかなり悪い例を示したものである。このようなものでは，新品時放電量Ｑｎと放電量ＱＭとの差は，経年劣化による部分とリチウム析出による部分との合計量となっている。なお，平均的な使用による電池２１の判定時の放電量Ｑは，図中の例に示すように，新品時放電量Ｑｎより小さく，同じ年月を経た経年放電量Ｑｒと同じかそれよりやや小さいものとなる。   Further, when both the aging deterioration and the deterioration due to lithium deposition proceed considerably, as shown by the solid line L4 in FIG. 3, the discharge amount QM becomes smaller than the broken line L2 and the broken line L3. This is a pretty bad example. In such a case, the difference between the discharge amount Qn at the time of a new article and the discharge amount QM is the total amount of the portion due to aging and the portion due to lithium deposition. It should be noted that the discharge amount Q at the time of determination of the battery 21 due to average use is smaller than the new discharge amount Qn, as shown in the example in the figure, and is the same as or slightly higher than the aged discharge amount Qr after the same age. It will be small.

本形態では，放電量取得部１２において，放電量Ｑを取得するとともに，新品時放電量取得部１６によって取得されている新品時放電量Ｑｎと判定時の電池２１の放電量Ｑとの差も取得する。この差は，電池２１の放電量が，使用や経年によって低下した程度を表す。以下では，この差（すなわち放電量Ｑの低下分）を低下放電量ΔＱという（図３参照）。この低下放電量ΔＱは，次式によって求められる。
ΔＱ ＝ Ｑｎ − Ｑ …（式１） In the present embodiment, the discharge amount acquisition unit 12 acquires the discharge amount Q, and also the difference between the new discharge amount Qn acquired by the new discharge amount acquisition unit 16 and the discharge amount Q of the battery 21 at the time of determination. get. This difference represents the degree to which the discharge amount of the battery 21 has decreased due to use and aging. Hereinafter, this difference (that is, the decrease in the discharge amount Q) is referred to as a decrease discharge amount ΔQ (see FIG. 3). This reduced discharge amount ΔQ is obtained by the following equation.
ΔQ = Qn−Q (Formula 1)

一方，このうちの経年劣化による分が，電池２１と同じ年月を経た経年劣化電池２１ｒの放電量であり，経年放電量Ｑｒである。そして，新品時放電量Ｑｎと経年放電量Ｑｒとの差が，図３に示す経年低下放電量ΔＱｒである。この経年低下放電量ΔＱｒは，次式で表される。
ΔＱｒ ＝ Ｑｎ − Ｑｒ …（式２） On the other hand, the amount due to aging of these is the discharge amount of the aging battery 21r that has passed the same age as the battery 21, and is the aging discharge amount Qr. The difference between the new discharge amount Qn and the aged discharge amount Qr is the aged decrease discharge amount ΔQr shown in FIG. This age-decreasing discharge amount ΔQr is expressed by the following equation.
ΔQr = Qn−Qr (Formula 2)

そして，式１で得られる低下放電量ΔＱから，式２で得られる経年低下放電量ΔＱｒを除いた分が，リチウム析出による放電量の低下分（以下では，「析出低下放電量ΔＱｃ」という）である。図３に示すように，低下放電量ΔＱと経年低下放電量ΔＱｒとの差が析出低下放電量ΔＱｃであり，次式で表される。
ΔＱｃ ＝ ΔＱ − ΔＱｒ …（式３） Then, the amount obtained by subtracting the amount of aging decrease discharge ΔQr obtained by equation 2 from the decrease discharge amount ΔQ obtained by equation 1 is the decrease in discharge amount due to lithium deposition (hereinafter referred to as “deposition decrease discharge amount ΔQc”). It is. As shown in FIG. 3, the difference between the reduced discharge amount ΔQ and the aged decrease discharge amount ΔQr is the deposition reduced discharge amount ΔQc, which is expressed by the following equation.
ΔQc = ΔQ−ΔQr (Expression 3)

これらのうち，経年低下放電量ΔＱｒは，図２に示したように，内部抵抗値Ｒに対応して変化する。図中で左上の新品時には，放電量は新品時放電量Ｑｎであり，内部抵抗値はＲｎである。経年劣化が進行すると，内部抵抗値Ｒは上昇し，放電量Ｑは減少する。そして，新品時放電量Ｑｎと，内部抵抗値Ｒに対応する経年放電量Ｑｒとの差が，経年低下放電量ΔＱｒである。従って，経年低下放電量ΔＱｒは，内部抵抗値Ｒと図２とから求めることができる。   Among these, the aging-decreasing discharge amount ΔQr changes corresponding to the internal resistance value R as shown in FIG. In the case of a new product in the upper left in the figure, the discharge amount is the discharge amount Qn when new, and the internal resistance value is Rn. As the aging progresses, the internal resistance value R increases and the discharge amount Q decreases. The difference between the discharge amount Qn when new and the aging discharge amount Qr corresponding to the internal resistance value R is the aging decrease discharge amount ΔQr. Therefore, the aging reduction discharge amount ΔQr can be obtained from the internal resistance value R and FIG.

すなわち，内部抵抗値Ｒと経年低下放電量ΔＱｒとの間には，図４に示すように，一定の相関関係がある。新品時には内部抵抗値ＲはＲｎであり，経年劣化により，内部抵抗値Ｒと経年低下放電量ΔＱｒとはともに上昇する。この関係をマップ化したものが相関マップ１７である。なお，この図４のグラフの形状は，式３から明らかではあるが，図２のグラフを上下反転した形である。   That is, there is a certain correlation between the internal resistance value R and the aging discharge amount ΔQr, as shown in FIG. When the product is new, the internal resistance value R is Rn, and both the internal resistance value R and the aging decrease discharge amount ΔQr increase due to aging. A map obtained by mapping this relationship is a correlation map 17. The shape of the graph of FIG. 4 is apparent from Equation 3, but is a vertically inverted version of the graph of FIG.

本形態の相関マップ１７は，電池２１と同種の電池についての内部抵抗値Ｒと経年低下放電量ΔＱｒとの関係をマップ化したものである。本形態では，予め実験等により相関マップ１７を作成し，相関マップ記憶部１４に記憶させている。本形態の析出判定部１５は，この相関マップ１７を参照することにより，内部抵抗取得部１３によって取得される内部抵抗値Ｒに対応する経年低下放電量ΔＱｒを得る。   The correlation map 17 of this embodiment is a map of the relationship between the internal resistance value R and the aging deterioration discharge amount ΔQr for the same type of battery as the battery 21. In this embodiment, a correlation map 17 is created in advance by experiments or the like and stored in the correlation map storage unit 14. The deposition determination unit 15 of the present embodiment refers to the correlation map 17 to obtain the aged decrease discharge amount ΔQr corresponding to the internal resistance value R acquired by the internal resistance acquisition unit 13.

さらに本形態の析出判定部１５は，放電量取得部１２によって得られる低下放電量ΔＱと，相関マップ１７から得られる経年低下放電量ΔＱｒとの差を取ることにより，式３のように，析出低下放電量ΔＱｃを得る。析出判定部１５は析出低下放電量ΔＱｃの大きさに基づいて，リチウム析出の程度を判定する。すなわち，この値が大きいほどリチウム析出の程度が大きく，この値が小さいほどリチウム析出の程度が小さいと判定される。   Further, the deposition determination unit 15 of the present embodiment takes the difference between the reduced discharge amount ΔQ obtained by the discharge amount acquisition unit 12 and the aged decrease discharge amount ΔQr obtained from the correlation map 17 to obtain the precipitation as shown in Equation 3. A reduced discharge amount ΔQc is obtained. The deposition determining unit 15 determines the degree of lithium deposition based on the magnitude of the deposition decreasing discharge amount ΔQc. That is, it is determined that the greater the value, the greater the degree of lithium deposition, and the smaller the value, the smaller the degree of lithium deposition.

なお，析出判定部１５によって，リチウム析出の量が予め定めた閾値等の基準値より多いと判断された場合には，許容できない程度までリチウム析出が進んでいると推定される。このようになった電池２１を使い続けることは好ましくない。そこで，例えば表示装置等を利用して，ユーザに電池２１の交換を促すメッセージや警告表示等を行うことが好ましい。   When the precipitation determining unit 15 determines that the amount of lithium deposition is larger than a reference value such as a predetermined threshold value, it is estimated that lithium deposition has progressed to an unacceptable level. It is not preferable to continue to use the battery 21 having such a configuration. Therefore, it is preferable to use a display device or the like to display a message, a warning display, or the like prompting the user to replace the battery 21.

図１の電池システム１０による判定は，次の手順１〜４によって行われる。
手順１．放電量Ｑの測定
手順２．低下放電量ΔＱの取得
手順３．内部抵抗値Ｒの取得
手順４．リチウム析出程度の判定
以下，順に説明する。 The determination by the battery system 10 of FIG. 1 is performed by the following procedures 1 to 4.
Procedure 1. Procedure for measuring discharge amount Q2. 2. Procedure for obtaining reduced discharge amount ΔQ 3. Procedure for obtaining internal resistance value R The determination of the degree of lithium deposition will be described in order.

手順１．放電量Ｑの測定
この手順では，電池２１を診断開始電圧Ｖｓから診断終了電圧Ｖｅまで放電させ，その間の累積の放電量Ｑを取得する。そのために，まず，電圧制御部１１によって電池２１の現在の電圧値Ｖｏを取得し，電圧値Ｖｏが診断開始電圧Ｖｓとなるまで，電池２１の放電または充電を行う。なお，この放電または充電のための構成も電池システム１０に含まれるものとしてもよい。あるいは，電池システム１０とは別に，電池２１を充放電できる装置を有するものであってもよい。 Procedure 1. Measurement of Discharge Amount In this procedure, the battery 21 is discharged from the diagnosis start voltage Vs to the diagnosis end voltage Ve, and the cumulative discharge amount Q during that time is acquired. For this purpose, first, the current voltage value Vo of the battery 21 is acquired by the voltage control unit 11, and the battery 21 is discharged or charged until the voltage value Vo reaches the diagnosis start voltage Vs. The configuration for discharging or charging may also be included in the battery system 10. Alternatively, a device that can charge and discharge the battery 21 may be provided separately from the battery system 10.

電池２１の電圧値Ｖｏが診断開始電圧Ｖｓとなったら，電圧制御部１１は，電流値Ｉを比較的低電流の一定値となるように制御しつつ，電池２１の電圧値Ｖｏが診断終了電圧Ｖｅとなるまで電池２１を放電させる。そして，放電量取得部１２によって，電流値×放電時間を積算し，判定時の電池２１の放電量Ｑを取得する。   When the voltage value Vo of the battery 21 becomes the diagnosis start voltage Vs, the voltage control unit 11 controls the current value I to be a constant value of a relatively low current, while the voltage value Vo of the battery 21 becomes the diagnosis end voltage. The battery 21 is discharged until Ve is reached. Then, the discharge amount acquisition unit 12 integrates the current value × discharge time to acquire the discharge amount Q of the battery 21 at the time of determination.

手順２．低下放電量ΔＱの取得
放電量取得部１２は，手順１で得られた放電量Ｑを，放電量取得部１２に記憶されている新品時放電量Ｑｎと比較し，前述の式１によって低下放電量ΔＱを取得する。 Procedure 2. Acquisition of reduced discharge amount ΔQ The discharge amount acquisition unit 12 compares the discharge amount Q obtained in the procedure 1 with the new discharge amount Qn stored in the discharge amount acquisition unit 12 and reduces the discharge amount according to the above-described equation 1. Get the quantity ΔQ.

そのために，本形態の新品時放電量取得部１６は，電池システム１０を有する装置に，新たな電池２１が取り付けられた場合に，その使用を開始する前に診断開始電圧Ｖｓから診断終了電圧Ｖｅまでの放電による放電量を取得して記憶しておく。新品時放電量Ｑｎの取得方法は，放電量取得部１２で放電量Ｑを取得する際に行うものと同様である。または，この電池システム１０に電池２１が取り付けられる以前に，当該電池２１の新品時放電量Ｑｎを同じ方法で予め取得しておき，その取得された値を新品時放電量取得部１６に記憶させるようにしてもよい。あるいは，同種のものであれば電池による個体差はほとんど無いという場合には，使用する電池の種類に応じて固定値として記憶しておいてもよい。   For this reason, when the new battery 21 is attached to the apparatus having the battery system 10, the new-time discharge amount acquisition unit 16 of the present embodiment uses the diagnosis end voltage Ve from the diagnosis start voltage Vs before starting the use. The amount of discharge due to the discharge until is acquired and stored. The method of acquiring the new-time discharge amount Qn is the same as that performed when the discharge amount acquisition unit 12 acquires the discharge amount Q. Alternatively, before the battery 21 is attached to the battery system 10, the new battery discharge amount Qn of the battery 21 is acquired in advance by the same method, and the acquired value is stored in the new battery discharge amount acquisition unit 16. You may do it. Alternatively, if there is almost no individual difference between batteries as long as they are of the same type, they may be stored as a fixed value according to the type of battery used.

手順３．内部抵抗値Ｒの取得
さらに，内部抵抗取得部１３によって，診断時の電池２１の内部抵抗値Ｒを取得する。電池の内部抵抗値は，使用状況や環境等の影響で新品電池から次第に増大する。本形態では，例えば手順１の過程で得られる電圧値と電流値との組を２組以上用いて，内部抵抗値Ｒを取得することができる。なお，車両に搭載している電池２１の場合は，走行中に随時，電圧値と電流値との組を測定することにより，さらに精度のよい測定が可能である。この測定方法については，後述する。なお，この手順は次の手順４より以前に終わっていればよく，その実行時期は特に限定されない。 Procedure 3. Acquisition of Internal Resistance Value R Furthermore, the internal resistance acquisition unit 13 acquires the internal resistance value R of the battery 21 at the time of diagnosis. The internal resistance value of a battery gradually increases from that of a new battery due to the influence of usage conditions and environment. In this embodiment, for example, the internal resistance value R can be acquired by using two or more sets of voltage values and current values obtained in the procedure 1. In the case of the battery 21 mounted on the vehicle, more accurate measurement is possible by measuring a set of voltage value and current value at any time during traveling. This measuring method will be described later. This procedure only needs to be completed before the next procedure 4, and the execution time is not particularly limited.

手順４．リチウム析出程度の判定
次に，析出判定部１５は，相関マップ記憶部１４に記憶されている相関マップ１７から，手順３で得られた内部抵抗値Ｒに対応する経年低下放電量ΔＱｒを読み出す。相関マップ１７には，図４に示したような，内部抵抗値Ｒと経年低下放電量ΔＱｒとの関係をマップ化したものが記憶されているので，手順３で得られた内部抵抗値Ｒに基づいて経年低下放電量ΔＱｒを読み出すことができる。 Procedure 4. Determination of Lithium Deposition Degree Next, the precipitation determination unit 15 reads the aging decrease discharge amount ΔQr corresponding to the internal resistance value R obtained in the procedure 3 from the correlation map 17 stored in the correlation map storage unit 14. Since the correlation map 17 stores a map of the relationship between the internal resistance value R and the aging discharge amount ΔQr as shown in FIG. 4, the internal resistance value R obtained in step 3 is stored in the correlation map 17. Based on this, it is possible to read out the aging decrease discharge amount ΔQr.

ここで得られる経年低下放電量ΔＱｒは，式２に示すように，リチウム析出がなく，経年劣化のみによる放電量の低下量に相当するものである。そして，手順２で得られた低下放電量ΔＱは，これと，リチウム析出による放電量の低下量との合計である。従って，これらの差から，上記の式３に示したように，リチウム析出の量に対応する分の析出低下放電量ΔＱｃを得ることができる。   The aged discharge amount ΔQr obtained here corresponds to a decrease amount of the discharge amount due to only aged deterioration without lithium deposition as shown in Equation 2. The reduced discharge amount ΔQ obtained in the procedure 2 is the sum of this and the decrease amount of the discharge amount due to lithium deposition. Therefore, from these differences, as shown in Equation 3 above, it is possible to obtain a precipitation-decreasing discharge amount ΔQc corresponding to the amount of lithium deposition.

例えば，図５に矢印ａで示すように，内部抵抗値Ｒと相関マップ１７とから，経年低下放電量ΔＱｒを求め，低下放電量ΔＱとの差を取ることにより析出低下放電量ΔＱｃを得ることができる。このようにすることにより，診断対象である電池２１の低下放電量ΔＱのうち，経年劣化による経年低下放電量ΔＱｒの分を除いて，リチウム析出に起因する部分のみを抽出することができる。   For example, as indicated by an arrow a in FIG. 5, the amount of aging deterioration discharge ΔQr is obtained from the internal resistance value R and the correlation map 17, and the precipitation reduction discharge amount ΔQc is obtained by taking the difference from the decrease discharge amount ΔQ. Can do. By doing so, it is possible to extract only the portion due to lithium deposition, excluding the amount of aging decrease discharge amount ΔQr due to aging from the decrease discharge amount ΔQ of the battery 21 to be diagnosed.

リチウム析出が全くない場合には，低下放電量ΔＱと経年低下放電量ΔＱｒとは等しく，析出低下放電量ΔＱｃ＝０である。析出したリチウムの量が多いほど析出低下放電量ΔＱｃが大きい。図３上では，リチウム析出が進行するにつれて，放電量Ｑがより小さくなり，経年放電量Ｑｒから離れていくことになる。本形態の析出判定部１５は，得られた析出低下放電量ΔＱｃの値からリチウム析出の程度を判定する。従って，経年劣化の影響を排除して，リチウム析出の程度を高精度に判断することができる。   When there is no lithium deposition, the reduced discharge amount ΔQ is equal to the aged decrease discharge amount ΔQr, and the deposition decreased discharge amount ΔQc = 0. The greater the amount of lithium deposited, the greater the deposition drop discharge amount ΔQc. In FIG. 3, as the lithium deposition progresses, the discharge amount Q becomes smaller and moves away from the aged discharge amount Qr. The deposition determination unit 15 of this embodiment determines the degree of lithium deposition from the value of the obtained deposition decrease discharge amount ΔQc. Therefore, it is possible to determine the degree of lithium deposition with high accuracy by eliminating the influence of aging deterioration.

ここまでは，内部抵抗値Ｒと相関マップ１７とから，図５中の矢印ａで示すように，析出低下放電量ΔＱｃを得る方法を説明した。しかし，相関マップ１７の使い方はこれに限らない。例えば，図中に矢印ｂで示すように，得られた低下放電量ΔＱが経年劣化のみによるものであると仮定した場合の内部抵抗値Ｒｂを読み出すこともできる。そして，内部抵抗値ＲとＲｂとの差であるΔＲを用いて，リチウム析出の程度を判定することもできる。   Up to this point, the method of obtaining the precipitation decreasing discharge amount ΔQc from the internal resistance value R and the correlation map 17 as shown by the arrow a in FIG. 5 has been described. However, the usage of the correlation map 17 is not limited to this. For example, as indicated by an arrow b in the figure, it is also possible to read the internal resistance value Rb when it is assumed that the obtained reduced discharge amount ΔQ is only due to aging. The degree of lithium deposition can also be determined using ΔR, which is the difference between the internal resistance values R and Rb.

あるいは，図６に矢印ｃで示すように，得られた内部抵抗値Ｒに対応するマップ上の点ｐ１と，得られた低下放電量ΔＱに対応するマップ上の点ｐ２との比較から，これらのマップ上での差ΔＰを求め，この値に基づいてリチウム析出の程度を判定することもできる。例えば，マップ上に座標を振っておくことにより，この間の差を求めるようにしてもよい。いずれの例においても，得られた低下放電量ΔＱと得られた内部抵抗値Ｒとを，相関マップ１７を介して，少なくとも一方を変換することにより同一の尺度上で対比しているものである。   Alternatively, as indicated by an arrow c in FIG. 6, these points are obtained by comparing a point p1 on the map corresponding to the obtained internal resistance value R and a point p2 on the map corresponding to the obtained reduced discharge amount ΔQ. The difference ΔP on the map can be obtained, and the degree of lithium deposition can be determined based on this value. For example, the difference between them may be obtained by waving coordinates on the map. In either example, the obtained reduced discharge amount ΔQ and the obtained internal resistance value R are compared on the same scale by converting at least one through the correlation map 17. .

さらに，新品時放電量Ｑｎにバラツキがなく，固定値として扱うことができる場合には，判定時の放電量Ｑを直接，判定区間放電量の情報として用いることもできる。すなわち，放電量Ｑと経年放電量Ｑｒとの差を，そのまま析出低下放電量ΔＱｃであるとすることもできる。この場合には，新品時放電量取得部１６は無くてもよい。これに対して，ここまでに説明したように，低下放電量ΔＱを用いて経年劣化のみによるものと比較するシステムは，対象電池の判定区間放電量を補正して判定しているものである。あるいは，相関マップを補正して判定してもよいし，内部抵抗値を補正して判定してもよい。   Further, when there is no variation in the discharge amount Qn at the time of a new product and it can be handled as a fixed value, the discharge amount Q at the time of determination can be directly used as information on the determination section discharge amount. In other words, the difference between the discharge amount Q and the aged discharge amount Qr can be used as it is as the precipitation decreasing discharge amount ΔQc. In this case, the new discharge amount acquisition unit 16 may be omitted. On the other hand, as explained so far, the system that uses the reduced discharge amount ΔQ and compares it with the one caused only by aging deterioration is determined by correcting the determination section discharge amount of the target battery. Alternatively, the correlation map may be corrected for determination, or the internal resistance value may be corrected for determination.

なお，上記の形態の電池システム１０は，ハイブリッド自動車その他の自動車に搭載することができる。図７に本形態の電池システム１０を搭載したハイブリッド自動車１を示す。このハイブリッド自動車１は，車体２に，エンジン３，モータ４，電池パック５，コントローラ６を搭載したものである。電池パック５とモータ４とコントローラ６とは，ケーブル７により接続されている。電池パック５には，複数個の電池２１が内蔵されている。そして，コントローラ６には，本形態の電池システム１０が含まれている。すなわち，ハイブリッド自動車１においては，コントローラ６が電池システム１０を構成している。   The battery system 10 of the above embodiment can be mounted on a hybrid vehicle or other vehicles. FIG. 7 shows a hybrid vehicle 1 equipped with the battery system 10 of the present embodiment. In this hybrid vehicle 1, an engine 3, a motor 4, a battery pack 5, and a controller 6 are mounted on a vehicle body 2. The battery pack 5, the motor 4 and the controller 6 are connected by a cable 7. A plurality of batteries 21 are built in the battery pack 5. The controller 6 includes the battery system 10 of this embodiment. That is, in the hybrid vehicle 1, the controller 6 constitutes the battery system 10.

ハイブリッド自動車１は，エンジン３とモータ４とを併用して車輪を駆動するようになっている。本形態のハイブリッド自動車１では，電池パック５からモータ４へ電池の放電電流が供給され，モータ４が動力を発生するようになっている。また，ハイブリッド自動車１の走行状況によっては，モータ４で回生起電力が発生することがある。これにより電池パック５の電池へ充電電流が供給され，電池が充電されるようになっている。ここにおいて，コントローラ６が，電池パック５とモータ４との間の電流のやりとりを制御している。そのためにコントローラ６は，公知のインバータを内蔵している。   The hybrid vehicle 1 drives the wheels by using the engine 3 and the motor 4 together. In the hybrid vehicle 1 of the present embodiment, the battery discharge current is supplied from the battery pack 5 to the motor 4 so that the motor 4 generates power. Depending on the traveling state of the hybrid vehicle 1, regenerative electric power may be generated by the motor 4. Thereby, a charging current is supplied to the battery of the battery pack 5, and the battery is charged. Here, the controller 6 controls the exchange of current between the battery pack 5 and the motor 4. For this purpose, the controller 6 incorporates a known inverter.

このようなハイブリッド自動車１に搭載されている電池２１における，内部抵抗値Ｒの取得方法について説明する。上記の判定手順では，１．の過程で得られる電圧値と電流値との組を使用して内部抵抗値Ｒを得るとした。しかし，診断のための放電時には比較的一定の低電流での放電が行われるため，このようにして得られた電流値は，同程度の大きさのものばかりである。より高精度に内部抵抗値Ｒを取得するためには，内部抵抗値Ｒの算出に用いる電流値に，ある程度の幅があることが望ましい。   A method for obtaining the internal resistance value R in the battery 21 mounted in the hybrid vehicle 1 will be described. In the above determination procedure, 1. It was assumed that the internal resistance value R was obtained using a set of voltage value and current value obtained in the above process. However, since a discharge with a relatively constant low current is performed at the time of discharge for diagnosis, the current values obtained in this way are only of the same magnitude. In order to obtain the internal resistance value R with higher accuracy, it is desirable that the current value used for calculating the internal resistance value R has a certain range.

ハイブリッド自動車１に搭載されている電池２１では，走行中に充放電が行われる。そこで，走行中の放電期間中に電圧値と電流値との組を複数回測定し，記録しておくことができる。通常の走行では，電池２１から放電される電流値は一定に近いものではなく，状況に応じてかなり上下するため，ある程度の幅のある電流値が得られるからである。記録されたこれらの値の関係は，例えば図８に示すように表される。そこで，このグラフの傾きから，高精度に内部抵抗値Ｒを得ることができる。   The battery 21 mounted on the hybrid vehicle 1 is charged / discharged during traveling. Therefore, a set of voltage value and current value can be measured and recorded a plurality of times during the discharging period during traveling. This is because in normal traveling, the current value discharged from the battery 21 is not nearly constant, and varies considerably depending on the situation, so that a current value having a certain width can be obtained. The relationship between these recorded values is expressed as shown in FIG. 8, for example. Therefore, the internal resistance value R can be obtained with high accuracy from the slope of this graph.

ただし，車両に搭載されているコントローラ６では，測定した電流・電圧値のデータが失われたり，または信頼性に欠けている場合がないとはいえない。例えば，コントローラ６へ電力を供給する補機バッテリの抜けやデータの読み込みエラー等が原因で一旦記憶したデータが失われた場合や，長く走行していないため記憶されている電圧・電流値の測定時期が古い場合等である。このような場合には，電池２１の診断を行う前に別途，内部抵抗値Ｒを取得するとよい。すなわち，車両の走行とは関係なく，内部抵抗値Ｒの取得に適した程度の充電または放電を行い，そのときの電流・電圧値を測定してもよい。そして，取得した電流・電圧値から内部抵抗値Ｒを算出して診断に利用すれば，高精度な診断が可能である。   However, in the controller 6 mounted on the vehicle, it cannot be said that there is no case in which the measured current / voltage value data is lost or the reliability is lacking. For example, if the stored data is lost due to the loss of the auxiliary battery that supplies power to the controller 6 or the data reading error, or the stored voltage / current value is measured because it has not traveled for a long time. This is the case when the time is old. In such a case, the internal resistance value R may be obtained separately before the battery 21 is diagnosed. In other words, the current / voltage value at that time may be measured by performing charging or discharging at a level suitable for obtaining the internal resistance value R regardless of the traveling of the vehicle. If the internal resistance value R is calculated from the acquired current / voltage values and used for diagnosis, highly accurate diagnosis is possible.

なお本形態の車両としては，その動力源の全部あるいは一部に電池による電気エネルギを使用している車両であれば良く，ハイブリッド自動車に限られない。例えば，電気自動車，プラグインハイブリッド自動車，ハイブリッド鉄道車両，フォークリフト，電気車椅子，電動アシスト自転車，電動スクータ等であってもよい。   The vehicle of the present embodiment is not limited to a hybrid vehicle as long as the vehicle uses electric energy from a battery for all or a part of its power source. For example, an electric vehicle, a plug-in hybrid vehicle, a hybrid railway vehicle, a forklift, an electric wheelchair, an electric assist bicycle, an electric scooter, etc. may be used.

以上詳細に説明したように本形態の電池システムによれば，電池２１を診断開始電圧Ｖｓから診断終了電圧Ｖｅまで放電させて，放電量Ｑを取得する。そして，新品時放電量Ｑｎからの低下放電量ΔＱを得る。さらに，そのうちの経年劣化に相当する部分である経年低下放電量ΔＱｒを相関マップ１７から読み出して，低下放電量ΔＱとの差である析出低下放電量ΔＱｃを得る。この析出低下放電量ΔＱｃの大きさに基づいて，リチウム析出の程度を判定することができる。従って，劣化の進行した非水電解液型リチウムイオン二次電池のリチウム析出の程度を精度よく判定できる。   As described above in detail, according to the battery system of this embodiment, the battery 21 is discharged from the diagnosis start voltage Vs to the diagnosis end voltage Ve, and the discharge amount Q is acquired. Then, a reduced discharge amount ΔQ from the discharge amount Qn when new is obtained. Further, the aging decrease discharge amount ΔQr, which is a portion corresponding to the aging deterioration, is read from the correlation map 17 to obtain the precipitation decrease discharge amount ΔQc which is the difference from the decrease discharge amount ΔQ. The degree of lithium deposition can be determined based on the magnitude of the deposition decreasing discharge amount ΔQc. Therefore, it is possible to accurately determine the degree of lithium deposition in the non-aqueous electrolyte type lithium ion secondary battery that has been deteriorated.

なお，本形態は単なる例示にすぎず，本発明を何ら限定するものではない。したがって本発明は当然に，その要旨を逸脱しない範囲内で種々の改良，変形が可能である。
例えば，内部抵抗値Ｒを取得するための電流・電圧値の測定時の環境温度と，診断時の環境温度とが大きく異なっている場合には，取得された内部抵抗値Ｒを温度に応じて補正するようにしてもよい。 In addition, this form is only a mere illustration and does not limit this invention at all. Therefore, the present invention can naturally be improved and modified in various ways without departing from the gist thereof.
For example, when the environmental temperature at the time of measuring the current / voltage value for acquiring the internal resistance value R and the environmental temperature at the time of diagnosis are greatly different, the acquired internal resistance value R is determined according to the temperature. You may make it correct | amend.

１ ハイブリッド自動車
５ 電池パック
６ コントローラ
１０ 非水電解液型リチウムイオン二次電池システム
１２ 放電量取得部
１３ 内部抵抗取得部
１５ 析出判定部
１６ 新品時放電量取得部
１７ 相関マップ
２１ 非水電解液型リチウムイオン二次電池 DESCRIPTION OF SYMBOLS 1 Hybrid vehicle 5 Battery pack 6 Controller 10 Nonaqueous electrolyte type lithium ion secondary battery system 12 Discharge amount acquisition part 13 Internal resistance acquisition part 15 Precipitation determination part 16 New time discharge amount acquisition part 17 Correlation map 21 Nonaqueous electrolyte type Lithium ion secondary battery

Claims (7)

非水電解液型リチウムイオン二次電池を予め定めた判定開始電圧から予め定めた判定終了電圧まで放電させたときの放電量（以下，「判定区間放電量」という）を取得する放電量取得部と，
非水電解液型リチウムイオン二次電池の内部抵抗値を取得する内部抵抗取得部と，
判定対象の非水電解液型リチウムイオン二次電池（以下，「対象電池」という）と同種の電池であってリチウム析出の起こっていないものにおける，内部抵抗値と判定区間放電量の情報との組合せを，電池の経時劣化の程度ごとに記録した相関マップと，
対象電池について判定時に前記放電量取得部で取得した判定区間放電量と，対象電池について判定時に前記内部抵抗取得部で取得した内部抵抗値とを，前記相関マップを介して少なくとも一方を変換することにより同一の尺度上で対比して，対象電池におけるリチウム析出の程度を判定する析出判定部とを有することを特徴とする非水電解液型リチウムイオン二次電池システム。 A discharge amount acquisition unit for acquiring a discharge amount (hereinafter referred to as “determination section discharge amount”) when discharging a non-aqueous electrolyte type lithium ion secondary battery from a predetermined determination start voltage to a predetermined determination end voltage When,
An internal resistance acquisition unit for acquiring the internal resistance value of the non-aqueous electrolyte type lithium ion secondary battery;
Information on the internal resistance value and information on the amount of discharge in the judgment section in the same type of battery as the non-aqueous electrolyte type lithium ion secondary battery (hereinafter referred to as “target battery”) that is subject to judgment, and in which lithium deposition has not occurred. A correlation map that records the combinations for each degree of battery aging,
At least one of the determination section discharge amount acquired by the discharge amount acquisition unit at the time of determination for the target battery and the internal resistance value acquired by the internal resistance acquisition unit at the time of determination for the target battery is converted via the correlation map. A non-aqueous electrolyte type lithium ion secondary battery system comprising: a deposition determination unit that determines the degree of lithium deposition in the target battery in comparison with the same scale. 請求項１に記載の非水電解液型リチウムイオン二次電池システムにおいて，
前記内部抵抗取得部は，前記放電量取得部による放電量の取得のための放電時の電流値と電圧値とから内部抵抗値の取得を行うことを特徴とする非水電解液型リチウムイオン二次電池システム。 The nonaqueous electrolyte type lithium ion secondary battery system according to claim 1,
The internal resistance acquisition unit acquires an internal resistance value from a current value and a voltage value during discharge for acquiring a discharge amount by the discharge amount acquisition unit. Next battery system. 請求項１または請求項２に記載の非水電解液型リチウムイオン二次電池システムにおいて，
対象電池の新品時の判定区間放電量を取得する新品時放電量取得部を有し，
前記析出判定部は，前記新品時放電量取得部が取得した判定区間放電量（以下，「新品時判定区間放電量」という）に基づいて，対象電池の判定時の判定区間放電量と，対象電池の判定時の内部抵抗値と，前記相関マップとの３者のうち１つを補正した上で判定を行うことを特徴とする非水電解液型リチウムイオン二次電池システム。 The non-aqueous electrolyte type lithium ion secondary battery system according to claim 1 or 2,
A new battery discharge amount acquisition unit that acquires the discharge amount of the judgment battery when the target battery is new;
The deposition determination unit is configured to determine a determination interval discharge amount at the time of determination of a target battery based on a determination interval discharge amount acquired by the new discharge amount acquisition unit (hereinafter referred to as a “new determination interval discharge amount”), A non-aqueous electrolyte type lithium ion secondary battery system, wherein the determination is performed after correcting one of the internal resistance value at the time of battery determination and the correlation map. 請求項３に記載の非水電解液型リチウムイオン二次電池システムにおいて，
前記相関マップは，前記判定区間放電量の情報として，新品時判定区間放電量と判定区間放電量との差の値（以下，「減少放電量」という）を用いるものであり，
前記析出判定部は，
対象電池の判定時の減少放電量と，対象電池の判定時の内部抵抗値に基づいて前記相関マップから読み出された判定区間放電量の情報と，の差の値（以下，「追加減少分」という）に応じて，
追加減少分が大きい場合はリチウム析出の程度が大きく，追加減少分が小さい場合はリチウム析出の程度が小さいと判定することを特徴とする非水電解液型リチウムイオン二次電池システム。 The non-aqueous electrolyte type lithium ion secondary battery system according to claim 3,
The correlation map uses, as information on the determination section discharge amount, a difference value between the determination section discharge amount and the determination section discharge amount when new (hereinafter referred to as “decreasing discharge amount”),
The precipitation determination unit
The difference value between the decrease discharge amount at the time of determination of the target battery and the information on the determination section discharge amount read from the correlation map based on the internal resistance value at the determination of the target battery (hereinafter referred to as “additional decrease amount”). ")
A non-aqueous electrolyte type lithium ion secondary battery system characterized in that when the additional decrease is large, the degree of lithium deposition is large, and when the additional decrease is small, the degree of lithium deposition is small. 対象電池と同種の電池であってリチウム析出の起こっていないものにおける，内部抵抗値と判定区間放電量の情報との組合せを，電池の経時劣化の程度ごとに記録した相関マップを有し，
対象電池について，判定時に判定区間放電量と内部抵抗値とを取得し，
取得した判定区間放電量と，取得した内部抵抗値とを，前記相関マップを介して少なくとも一方を変換することにより同一の尺度上で対比して，対象電池におけるリチウム析出の程度を判定することを特徴とする非水電解液型リチウムイオン二次電池システムにおけるリチウム析出判定方法。 It has a correlation map that records the combination of the internal resistance value and the information on the amount of discharge in the judgment section for each degree of deterioration of the battery in the same type of battery as the target battery, where lithium deposition does not occur,
For the target battery, obtain the discharge amount and internal resistance value during the determination,
Determining the degree of lithium deposition in the target battery by comparing the acquired determination interval discharge amount and the acquired internal resistance value on the same scale by converting at least one of them through the correlation map. A method for determining lithium deposition in a non-aqueous electrolyte type lithium ion secondary battery system. 請求項１から請求項４までのいずれか１つに記載の非水電解液型リチウムイオン二次電池システムを搭載する車両。 A vehicle on which the nonaqueous electrolyte type lithium ion secondary battery system according to any one of claims 1 to 4 is mounted. 請求項６に記載の車両において，
走行中に非水電解液型リチウムイオン二次電池の電圧値と電流値との組を測定するとともに取得された前記組を記憶する電圧電流取得部を有し，
前記内部抵抗取得部は，前記電圧電流取得部に２以上の前記組が記憶されている場合には，前記電圧電流取得部に記憶されている前記組に基づいて内部抵抗値を取得するとともに，それ以外の場合には，走行しない状態で非水電解液型リチウムイオン二次電池の充放電を行うことによって複数個の電圧電流値の組を取得し，その値に基づいて内部抵抗値を取得することを特徴とする車両。 The vehicle according to claim 6,
A voltage / current acquiring unit for measuring a set of voltage and current values of the non-aqueous electrolyte type lithium ion secondary battery during traveling and storing the acquired set;
When the two or more sets are stored in the voltage / current acquisition unit, the internal resistance acquisition unit acquires an internal resistance value based on the set stored in the voltage / current acquisition unit, and In other cases, a set of a plurality of voltage / current values is obtained by charging / discharging the non-aqueous electrolyte type lithium ion secondary battery without running, and the internal resistance value is obtained based on the value. A vehicle characterized by that.
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